Toward catalyst economy: A programmed approach to the synthesis of bicyclic lactones and lactams

Edlin, Chris D.; Faulkner, James; Fengas, David; Helliwell, Madeleine; Knight, Christopher K.; House, David; Parker, Jeremy S.; Preece, Ian; Quayle, Peter; Raftery, James; Richards, Stuart N.

doi:10.1016/j.jorganchem.2006.08.017

Cited by 19 publications

(8 citation statements)

References 28 publications

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“…However, this process does not strictly match with the definition of a tandem reaction. Quayle [57] has described the cross metathesis (CM) reaction of two alkenes followed by the an ATRC reaction (Scheme 17). Similarly, Delaude's group has described the use of homobimetallic ruthenium-indenylidene complex as catalyst for tandem metathesis / ATRC reactions.…”

Section: Tandem Atom Transfer Radical Reactionsmentioning

confidence: 99%

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

2011

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Transition‐metal‐catalyzed atom transfer radical reactions of halogenated compounds with olefins constitute a versatile tool in organic synthesis within the area of C–C bond forming transformations. The inter‐ or intramolecular versions, atom transfer radical addition (ATRA) or cyclization (ATRC), respectively, lead to the atom‐economic, useful synthesis of compounds that can be further functionalized. This contribution summarizes the recent developments in this area in terms of catalyst design as well as the applicability of this methodology in sequential, domino, or tandem reactions.

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Section: Tandem Atom Transfer Radical Reactionsmentioning

confidence: 99%

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

2011

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“…Copper(I),19 ruthenium(II)20 or sporadically iron(II)19t,21 are the typical metal ions used to catalyse these transformations. A number of interesting natural and unnatural products, have been prepared by this method,19a and useful domino processes, involving ATRC, have also been developed 17g,19a,k,q,u,20a,c,e…”

Section: Introductionmentioning

confidence: 99%

Efficient and Green Route to γ‐Lactams by Copper‐Catalysed Reversed Atom Transfer Radical Cyclisation of α‐Polychloro‐N‐allylamides, using a Low Load of Metal (0.5 mol%)

et al. 2013

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The cyclisation of N-allyl-N-substituteda-\ud polychloroamides is efficiently obtained through\ud a copper-catalysed activators regenerated by electron\ud transfer–atom transfer radical cyclisation process,\ud with a metal load of only 0.5 mol%. The redox\ud catalyst is introduced in its inactive form as copper(\ud II) chloride/[nitrogen ligand] complex, and continuously\ud regenerated to the active copper(I) chloride/[\ud nitrogen ligand] species by ascorbic acid. To\ud preserve the catalyst integrity, the hydrochloric\ud acid, released after each regeneration cycle, has\ud been quenched by carbonate. The choice of the solvent\ud is critical, the best performance being observed\ud in ethyl acetate-ethanol (3:1)

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“…Under these conditions, 1 H NMR analysis unambiguously revealed the formation of cyclopentadiene instead of the expected bicyclic lactone. The decomposition of cyclopentenyl trichloroacetate 17 into cyclopentadiene and trichloroacetic acid was already observed by Quayle et al under similar conditions [13–14]. These authors successfully trapped the diene via a Diels–Alder reaction with maleic anhydride.…”

Section: Resultsmentioning

confidence: 60%

“…This process, known as assisted tandem catalysis [ 6 ], presents significant advantages over multistep synthesis for increasing molecular complexity, particularly in terms of time- and cost-savings, atom economy, environmental friendliness, or applicability to diversity-oriented high-throughput synthesis [ 7 – 10 ]. The monometallic ruthenium–benzylidene complex [RuCl 2 (=CHPh)(PCy 3 ) 2 ] ( 3 ) and its second- or even third-generation analogues developed by Grubbs and co-workers are prominent examples of catalyst precursors that were applied to olefin metathesis in tandem with ATRA [ 11 ], ATRC [ 11 – 14 ], ATRP [ 15 – 18 ], cyclopropanation [ 19 ], dihydroxylation [ 20 ], hydrogenation [ 21 – 23 ], hydrovinylation [ 24 ], isomerization [ 25 – 28 ], oxidation [ 29 ], or Wittig reactions [ 30 ], to name just a few [ 31 ].…”

Section: Introductionmentioning

confidence: 99%

Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

Borguet¹,

Sauvage²,

Zaragoza³

et al. 2010

Beilstein J. Org. Chem.

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SummaryThe tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymene)Ru(μ-Cl)3RuCl(3-phenyl-1-indenylidene)(PCy3)] (1) to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II)–Ru(III) mixed-valence compound [(p-cymene)Ru(μ-Cl)3RuCl2(PCy3)], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.

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Toward catalyst economy: A programmed approach to the synthesis of bicyclic lactones and lactams

Cited by 19 publications

References 28 publications

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

Efficient and Green Route to γ‐Lactams by Copper‐Catalysed Reversed Atom Transfer Radical Cyclisation of α‐Polychloro‐N‐allylamides, using a Low Load of Metal (0.5 mol%)

Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

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